Inter-Rydberg spectroscopy of argon and neon dimers

Rydberg $\gets$ Rydberg transitions of Ar$\sb2$ and Ne$\sb2$ have been observed for the first time by laser-excitation spectroscopy. Molecular Rydbergs converging to the $A\sp2\Sigma\sbsp{1/2\rm u}{+}$ ion core having principal quantum numbers as large as 26 for Ar$\sb2$ and 17 for Ne$\sb2$ have been observed despite the predissociative nature of the high-lying Ar$\sb2$ and Ne$\sb2$ Rydbergs. The most prominent Rydberg series have been identified as the npπ\sb{\rm u} $\gets$ msσ\sb{\rm g} (Ar: m = 4, 5 $\leq$ n $\leq$ 26; Ne: m = 3, 4 $\leq$ n $\leq$ 17). The adiabatic ionization limits, relative to the lowest metastable state (4sσ\sb{\rm g}(1$\sb{\rm u}$, 0$\sbsp{\rm u}{-}$) for Ar$\sb2$, and 3sσ\sb{\rm g}\sp3\Sigma\sbsp{\rm u}{+} for Ne$\sb2$), were also determined to be 29373 $\pm$ 2 cm$\sp{-1}$ for Ar$\sb2$ and 34399 $\pm$ 3 cm$\sp{-1}$ for Ne$\sb2$. The associated npπ\sb{\rm u} $\gets$ msσ\sb{\rm g} (v$\sp\prime$, v$\sp{\prime\prime}$) = (0, 1) Rydberg series has also been observed (Ar: m = 4, 5 $\leq$ n $\leq$ 10; Ne: m = 3, 4 $\leq$ n $\leq$ 7) with ionization limits of 29079 $\pm$ 5 cm$\sp{-1}$ for Ar$\sb2$ and 33870 $\pm$ 20 cm$\sp{-1}$ for Ne$\sb2$. Two more Rydberg series have been observed in Ar$\sb2$ and assigned to be the npσ\sb{\rm u} and the nfπ\sb{\rm u} with the same series limit as the npπ\sb{\rm u} (29373 cm$\sp{-1}$). Also, several of the Rydberg $\gets$ Rydberg transitions in Ar$\sb2$ and Ne$\sb2$ have been rotationally resolved. This, to the knowledge of the author, is the first time any Rydberg $\gets$ Rydberg transitions have been rotationally resolved in the rare gas dimers heavier than He$\sb2$. Analysis of two of the bands indicate that B$\sb0$ $\simeq$ 0.17 cm$\sp{-1}$ for Ar$\sb2$4sσ\sb{\rm g}(1$\sb{\rm u}$, 0$\sbsp{\rm u}{-}$) and B$\sb0$ = 0.564 $\pm$ 0.007 cm$\sp{-1}$ for Ne$\sb2$3sσ\sb{\rm g}\sp3\Sigma\sbsp{\rm u}{+}. The photoionization cross section, as a function of wavelength, for the lowest metastable states have also been calculated from the data presented in this work.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Physics

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2011

Author dc:creator

• Kane, Daniel James

Contributors dc:contributor

• Eden, James G.

• Physics, Molecular

Statement dc:rights

• Copyright 1989 Kane, Daniel James

Language dc:language

eng

Identifier

AAI9010909
(UMI)AAI9010909

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/19740